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Cite as Nano-Micro Lett. (2021) 13:15 Received: 9 July 2020 Accepted: 29 September 2020 © The Author(s) 2020

https://doi.org/10.1007/s40820-020-00543-w

Controlled Assembly of Luminescent Lanthanide‑Organic Frameworks via  Post‑Treatment of 3D‑Printed Objects Jiahui Huang1, Peiyi Wu1,2 *

ARTICLE HIGHLIGHTS • Controlled 3D assembly of luminescent lanthanide metal–organic frameworks (LnMOFs) through additive manufacturing followed by posting-printing treatment, enabling the multiscale integration in a precisely controlled and facile manner. • 3D-printed LnMOFs objects with tunable fluorescence properties are caused by coordination and chelation of lanthanide ions, rendering a sub-millimeter resolution and high shape fidelity. • A type of 3D assembled LnMOFs-based optical sensing platform showing response to small molecules such as acetone is presented.

ABSTRACT  Complex multiscale assemblies of metal–

organic frameworks are essential in the construction of largescale optical platforms but often restricted by their bulk nature and conventional techniques. The integration of nanomaterials and 3D printing technologies allows the fabrication of multiscale functional architectures. Our study reports a unique method of controlled 3D assembly purely relying on the post-printing treatment of printed constructs. By immersing a 3D-printed patterned construct consisting of organic ligand in a solution of lanthanide ions, in situ growth of lanthanide metal–organic frameworks (LnMOFs) can rapidly occur, resulting in macroscopic assemblies and tunable fluorescence properties. This phenomenon, caused by coordination and chelation of lanthanide ions, also renders a sub-millimeter resolution and high shape fidelity. As a proof of concept, a type of 3D assembled LnMOFsbased optical sensing platform has demonstrated the feasibility in response to small molecules such as acetone. It is anticipated that the facile printing and design approach developed in this work can be applied to fabricate bespoke multiscale architectures of functional materials with controlled assembly, bringing a realistic and economic prospect. KEYWORDS  3D printing; Luminescent lanthanide-organic frameworks; Macroscopic assembly; In situ growth; Optical sensing

* Peiyi Wu, [email protected] 1 State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science and Laboratory of Advanced Materials, Fudan University, Shanghai 200433, People’s Republic of China 2 State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Chemistry, Chemical Engineering and Biotechnology, Center for Advanced Low‑Dimension Materials, Donghua University, Shanghai 201620, People’s Republic of China Vol.:(0123456789)

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1 Introduction Metal–organic frameworks (MOFs), a versatile class of crystalline solids composed of metal clusters and organic ligands via self-assembly, have been extensively explored for their rich structural chemistry and potential applications in various areas [1–4], espe